Polymerization nucleus fob



Patented Oct. 14, 1947 2.428.901 POLYMERIZATION NUoLEUs FOR wamxmnc OILS Gordon M. Williams, Dayton,

New Wrinkle, Inc., Wilmingt ration of Delaware Ohio, assignor to on, Del., a corpo- No Drawing. Application May 6, 1943, Serial No. 485,897

1 This invention relates to drying oils having the property of yielding wrinkle films when compounded with resins and driers to form a varnish and applied to a surface and dried.

More particularly, the present invention relates to means whereby polymerization nuclei may be initially formed whereby to improveor increase the drying rate and wrinkle forming properties of drying oils by treatment according to the present invention.

In the formation of surface wrinkles on a coata ing composition it is important that there be developed a considerable degree of strain caused by contraction or expansion, or both, between the surface layer and the body ofthe drying film.

While the mechanism of drying of coating films formation of polymerized units,-first on the surface layer and finally throughout the coating film, will aid materially in the speedy formation of the wrinkle texture or pattern which is desired. Furthermore, it is reasonable to assume that the more closely knit the polymerized associations are, the more uniform and pronounced will be the resulting wrinkle pattern or texture.

The exact manner in which the molecules of a drying oil orient themselves and interreact is not known. However, there is considerable evidence. to indicate that polar bodies are first formed by the introduction of oxygen into the points of unsaturation. These polar molecules are then able to polymerize and 'form'nuclei for further polymerization, and this gradual polymerzation' of polar molecules leads ultimately to the hardening of the coating film.

Furthermore, it is understood that the difference in drying characteristics between tung oil (China-wood oil) and other oils suchas linseed oil is largely due to the fact that the former by virtue of its high degree of conjugation and symmetry isable to form a closely knit three dimensional polymerized nucleus. Linseed oil and other similar oils, on the other hand, form drawn out polymerized units which are comparatively loosely knit.

The present invention deals particularly with means whereby the initial formation of poly- 7 Claims. (01. 106'222) merizing nuclei may be established in drying oils which are normally nonwrinkling in order to accelerate their drying rate and to improve and fully develop their wrinkle forming characteristics. This is brought about particularly by the introduction in said oils of organometallic compounds and metallic ions which serve to initiate polymerization and which tend largely to eliminate the necessity for the initial formation of polar bodies by means of oxidation of the oil. For, example, linseed oil and soya bean oil are considered to be normally nonwrinkling oils; however, if these oils are subjected to blowing they are readily transformed into wrinkling oils and the reason for this transformation is believed to be the formation of polar bodies due to the partial oxidation or the introduction of oxygen in the oil molecules,

It should be noted carefully that the selection of the metallic ion, as well as the corresponding organo radical is of considerable importance and will lead to g eat variations in the results to be attained. Experimentation has shown that principally only those metals of groups I, II and III in the periodic'table will react readily as such and in the form or organometallic compounds with the olefinic linkage to form a polymerizing nucleus. It is reasonable to expect, however, that most of the metals will react under the proper conditions. In some cases it may be necessary to use a catalyst and possibly a preliminary addition reaction in order to accomplish the correct 'attachment of the metallic ion to the olefinic bond.

It is important to note here the diflerence betweenthe construction of an oil molecule treated in this manner and the ordinary drier composition generally used in the art to accelerate drying of oils. In this case the metallic ions are attached to one or more carbons at their initial points of unsaturation either by means of organometallic compound or other chemical reactions which will serve to orient the metallic ion to this position, while in ordinary driers the me tallic ion is reacted with the acid group to form a C--O-M composition. The resulting difference in the polymerization is quite marked since the C'M linkage allows a much closer network of interreacting molecules than that experienced by any polymerization caused by driers of the general type now employed in the art.

of principal importance in the selection of an organo group is the formation of an organometallic compound which will unite readily with the oil to allow the initial polymerization. Forthe most part aliphatic groupings appear to be most satisfactory although in some cases aromatic and alicyclic radicals yield more desirable results.

Organometalllc compounds of the type employed according to the present invention are of the general formula RM where the It represents an aliphatic, aromatic or alicyclic radical which CaHr- H(CH2) r-GH:

metals, for instance, will add directly into the double bond and the resulting polymerization is similar to that pictured above. The initial stages of such a reaction may be illustrated as follows using the linolic acid radical and potassium:

and

The above reactions indicate that only one double bond has added the metal. It will be understood, of course, that undoubtedly there will be molecules in which the metal has added to both points of unsaturation.

The fundamental principles of the present invention are applicable to the treatment of other esters of drying oils besides the triglyceride formation. Typical of these are those obtained by the reaction of unsaturated fatty acids with monohydric alcohols and other polyhydric alcohols than trihydric. These substances possess potential drying properties which may be developed under proper conditions and which, with the aid of the polymerizing nucleus which results from the practice of the present invention will harden and produce suitable films.

Further, by way of illustration, and without thereby intending to limit the present invention, the following examples are given:

Example I 100 grams of linseed oil are placed in a suitable container provided with a cover, a gas inlet for furnishing a blanket of inert gas over the surface of the oil, a suitable condenser for condensing inflammable volatile matter, and a stirring device. Nitrogen gas is then introduced through the inlet at a slow but constant rate and 0.12 gram of CSC2H5 in 20 grams of diethyl ether is added. The stirrer is started and the contents allowed to react at room temperature for approximately 4 hours. The heat is then increased to approximately 50 C. for the removal of the ether and then to 200 C. at which temperature it is held for a period of about 4 hours until a rather viscous oil results. The nitrogen supply is shut oil approximately 1 hour prior to the completion of the cook.

The resulting product is a viscous oil possessing a highly increased drying rate and wrinkle forming properties which when compounded with resin and driers as is customary in the art will produce a coating composition which will yield a well defined uniform wrinkle film on application and drying. Example II 50 grams of an esterified mixture of linseed oil fatty acids and ethylene glycol are placed in a container such as described in Example I. 0.2

gram of C0(CH2-CH=CH2)2 in 20 grams of diethyl ether are then added to the container. Nitrogen is introduced to provide an inert blanket over the mixture and the stirrer is started. The contents are allowed to react for approximately 2 hours at room temperature and the temperature is then increased to approximately 50 C. for the removal of the ether and then to approximately 250 C. The mixture is maintained at this temperature for about 2 hours and 50 grams of the original ester is then added. At this point the temperature will rapidly drop, and it is then increased to 200 C. and kept at this level until the oil is quite viscous.

The product resulting from this treatment may be used in the usual manner in compounding wrinkle coating compositions and will produce oil.

, results not unlike those obtained with the product of Example 1.

Example III 100 grams of soya bean oil are placed in a container such as described in Example I and 0.15 gram of Pb(C3H7)2 added, and the mixture treated in the manner described in Example I. After the removal of the ether, however, the temperature is increased to 300 C. and maintained at that level for approximately 8 hours or until the oil reaches the desired degree of viscosity. The inert blanket of nitrogen is maintained throughout this treatment.

The product resulting from this treatment may be used in the same manner and will exhibit the same properties as the products resulting from the treatment of Examples I and II.

- Example IV 100 grams of soya bean oil are placed in a container such as described in Example I. A blanket of nitrogen is thrown over the surface of the oil whilethe latter is heated to a temperature of 120 C. to remove any water which may be present. The oil is then cooled to 0 C. with an ice Example V I To 100 grams of sunflower oil 0.15gram 01 finely divided copper is added in the manner described in Example IV with the exception that the copper may be added at room temperature'instead of at 0 C. The oil is then heated to 150 C. and held at that temperature for 3 hours with constant stirring and under a blanket of nitrogen.

The resulting product when compounded with resins and driers in a. varnish coating composition and applied and dried will exhibit better drying properties and wrinkling characteristics than.

similar compositions prepared from the untreated It will be understood that the foregoing examples are illustrative of the application of the method of the present invention, and that it is not intended to have the present invention limited to or circumscribed by the particular details of procedure, materials, or apparatus therein set forth or described in view of the tact that'the present invention is susceptible to modifications depending on individual preference and conditions without departing from the spirit of this disclosure and the scope of the appended claims.

This application is a. continuation-in-part of application Serial No. 485,646, filed May 4, 1943.

I claim:

' 1. The method 01' treating soya bean oil to increase its drying rate and transform it into a wrinkling oil which comprises heating 100 parts or said oil with 0.05 part or sodium at a temperature of about 120 C.

2. The method of treating soya bean oil to increase its drying rate and transform it into a wrinkling oil which comprises heating parts of said 011 in an inert ambient atmosphere at a temperature of C. to remove water there- 'from, cooling the oil to substantially 0 0., adding 0.05 part of sodium, permitting the temperature of the mixture to increase to room temperature and maintaining it at that temperature until no further reaction is evident, heating the mixture 'to a temperature of.120 C. with constant agitation, and holding the temperature of the mixture at this level for approximately 30 minutes.

3. The method of treating sunflower oil to increase its drying rate and convert it into a wrinkling oil which comprises heating said 011 with approximately 0.05 per cent of sodium metal at a maximum temperature of 120 C. for a time suflicient to produce an oil of the desired viscosity.

' 4. The method of treating sunflower oil to increase its drying rate and convert it into a wrinkling oil which comprises heating said oil with approximately 0.05 per cent of sodium metal at a. maximum temperature of C. for approximately3 hours with constant stirring and under a blanket of nitrogen.

5. The method of making a wrinkling composition comprising heating 100 parts of soya bean oil with 0.05 part of sodium at a temperatur of about 120 C. for approximately 30 minutes, and adding resin and drier to the treated oil.

6. The method .of making a wrinkling cc-mposi tion comprising heating a vegetable fatty oil with approximately 0.05 per cent sodium at a maximum temperature of 120 C. for approximately 40 minutes in an inert ambientatmosphere.

7. The method of making a wrinkling composition comprising heating 100 parts of soya, bean oil in an inert ambient atmosphere at a temperature of substantially 120 C. to remove water therefrom, cooling the oil to substantially 0 C., adding- 0.05 part of sodium, permitting the temperature of the mixture to increase to room temperature and maintaining it at room temperature until no further reaction is evident, heating the mixture to a temperature of substantially 120 C. with constant agitation and maintaining this temperature for approximately 30 minutes, and then adding resin and drier.

GORDON M. WILLIAMS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Great Britain Feb. 1, 1932 

